Ammonia → 2-Amino-4-chloro-5-methylbenzonitrile

HRID 47847ノート

反応式

HRID 47847 の反応式
Br[C:2]1[CH:8]=[C:7]([CH3:9])[C:6]([Cl:10])=[CH:5][C:3]=1[NH2:4].[Cu][C:12]#[N:13].N>CN1CCCC1=O>[C:12]([C:2]1[CH:8]=[C:7]([CH3:9])[C:6]([Cl:10])=[CH:5][C:3]=1[NH2:4])#[N:13]

参加物

5

反応物 3

HCID 222AmmoniaHCID 33346562-Bromo-5-chloro-4-methylanilineHCID 178418546HCID 178418546、化合物

生成物 1

HCID 108558652-Amino-4-chloro-5-methylbenzonitrile収率 66.4%

試薬・触媒・溶媒 1

HCID 13387N-methyl-2-pyrrolidone溶媒

実験手順

To a solution of 2-bromo-5-chloro-4-methylaniline (13.0 g 58.96 mmol) in N-methylpyrrolidinone (100 ml) was added copper(I) cyanide (10.56 g, 118 mmol). The reaction mixture was placed in an oil bath preheated to 163° C. and stirred at this temperature for 2 h. The reaction mixture was allowed to cool to room temperature and then poured in ice-water (300 ml) and aqueous ammonia (90 ml). The brown precipitate was collected by filtration, washed with water (150 ml), dissolved in dichloromethane and the insoluble material was removed by filtration. The filtrate was washed with brine (100 ml), dried (MgSO4) and concentrated in vacuo. Purification, on gradient elution with dichloromethane in petroleum ether 60-80° C. (65 to 95%), afforded a white solid (6.52 g), mp 180° C.; 1H-NMR (DMSO-d6) 2.14 (s, 3H, 4-CH3), 6.11 (s, 2H, NH2), 6.86 (s, 1H, 6-H), 7.39 (s, 1H, 3-H); MS (FAB, m/z) 166,168 [(M+H)+; 90%, 40% respectively; Cl isotopic pattern]; FAB-HRMS: measured 166.0307; calculated for C8H8ClN2 (M+H)+ 166.0298.

後処理

  1. customThe reaction mixture was placed in an oil bath
  2. custompreheated to 163° C.
  3. filtrationThe brown precipitate was collected by filtration
  4. washwashed with water (150 ml)
  5. dissolutiondissolved in dichloromethane
  6. customthe insoluble material was removed by filtration
  7. washThe filtrate was washed with brine (100 ml)
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated in vacuo
  10. customPurification
  11. washon gradient elution with dichloromethane in petroleum ether 60-80° C. (65 to 95%)

出典と根拠

ORDレコード
ord-fd14e7fc615443658bae30f67ef9eeae
出典データセット
uspto-grants-2004_03
特許番号
US06699861B1

反応ノート

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